US3230213A - Preparation of aminoguanidine derivatives - Google Patents
Preparation of aminoguanidine derivatives Download PDFInfo
- Publication number
- US3230213A US3230213A US211140A US21114062A US3230213A US 3230213 A US3230213 A US 3230213A US 211140 A US211140 A US 211140A US 21114062 A US21114062 A US 21114062A US 3230213 A US3230213 A US 3230213A
- Authority
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- United States
- Prior art keywords
- starch
- percent
- oxidized
- water
- aminoguanidine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical class NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 title description 7
- 235000013808 oxidized starch Nutrition 0.000 claims description 19
- 239000001254 oxidized starch Substances 0.000 claims description 12
- 150000007857 hydrazones Chemical class 0.000 claims description 5
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 4
- -1 CARBONYL GROUPS Chemical group 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000002091 cationic group Chemical group 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920002472 Starch Polymers 0.000 description 9
- 235000019698 starch Nutrition 0.000 description 9
- 239000008107 starch Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 description 4
- 229920002085 Dialdehyde starch Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- OTXHZHQQWQTQMW-UHFFFAOYSA-N (diaminomethylideneamino)azanium;hydrogen carbonate Chemical compound OC([O-])=O.N[NH2+]C(N)=N OTXHZHQQWQTQMW-UHFFFAOYSA-N 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 241000364057 Peoria Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- MXWHMTNPTTVWDM-NXOFHUPFSA-N mitoguazone Chemical compound NC(N)=N\N=C(/C)\C=N\N=C(N)N MXWHMTNPTTVWDM-NXOFHUPFSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
Definitions
- novel guanylhydrazone are particularly valuable as cationic agents for retention of dyes and pigments on cellulosic fibers and as compositions, particularly with the guanylhydrazones of the more highly oxidized dialdehyde starch starting materials, for providing dry and wet strength in paper by addition to cellulosic fibers prior to sheet formation.
- My novel guanylhydrazones gelatinize in hot water to produce dispersions which are positively charged and have a cationic efiect at various pH levels. They are thus substantive to negatively charged cellulosic fibers and to anionic pigments and dyes.
- products possessing cationic properties can be prepared by reacting the carbonyl groups in oxidized starches with soluble salts of aminoguanidine using aqueous acidic conditions. Under these conditions high yields of essentially colorless products are obtained with essentially no degradation of the oxidized starch molecule.
- the main object of this invention is the synthesis of new cationic hydrazones containing both primary amino and imino groupings by reaction in water of oxidized starches containing reactive carbonyl groups with soluble aminoguanidine salts under acidic conditions. Partial substitution of the carbonyl groups in substantially fully oxidized starches is preferred for economic reasons. Further objects will be apparent from the following detailed description.
- any water-soluble aminoguanidine salt with a water-insoluble oxidized starch in an acid aqueous system for at least one hour at a non-gelatinizing temperature within the range of 25 to about 40 C. using up to one-fifth part by weight of the aminoguanidine salt per part of the oxidized starch but preferably 0.5 percent to about 10 percent by weight.
- the water-insoluble oxidized starch is continuously stirred in the acid aqueous reaction mixture and is reacted in the granule state.
- the white product is isolated by filtration and washed with water before drying. The yields are quantitative.
- the carbonyl groups of the oxidized starches react with the aminoguanidine salts to form hydrazones. However, it is preferred to react only about 0.5 to 10 percent of the carbonyl groups present in the highly oxidized (dialdehyde) starches. Essentiallyallof-the carbonyl groups are preferred to be reacted in the oxystarches containing a low carbonyl content of up to about 6 percent, although only a portion of the carbonyl groups may be reacted.
- the highly oxidized starches as is Well known may be prepared by periodate oxidation of starch.
- the commercially available lowly oxidized starches are generally produced by hypochlorite or chlorine oxidation of corn starch or other starches such as those of potato, wheat, sorghum, and tapioca.
- Example 1 25 grams of dialdehyde starch (corn starch oxidized with periodic acid to 93 percent dialdehyde content) was stirred in ml. of water at room temperature. To the continuously stirred slurry was added 25 ml. of an aqueous solution of aminoguanidine hydrochloride prepared by acidification of 2.5 grams of commercial aminoguanidine bicarbonate with hydrochloric acid. The pH of the reaction mixture was about 3. Reaction was continued at room temperature for 16 hours when the mixture was filtered or centrifuged off. The white product was washed with water and then with methanol and dried at 40 C. overnight. The recovery of white product was 27.4 grams. Nitrogen content was 2.99 percent (dry basis). Moisture was 13.1 percent.
- the nitrogen content showed that about 5 percent of the carbonyl groups of the dialdehyde starch had reacted with aminoguanidine hydrochloride to form a partial hydrazone.
- Example 2 Nitrogen to cellulosic pulp, and gave the pulp a positive charge.
- the treated pulp highly absorbed an anionic dye from solution.
- Example 3 36 grams of a commercial hypochlorite oxidized starch was slurried in 100 m1. of water and 25 ml. of water containing aminoguanidine hydrochloride prepared by acidification of 2.72 grams of aminoguanidine bicarbonate to pH 2. The mixture was stirred at room temperature for 20 hours and filtered. After 2 washings with water the white product was dried at 40 C. The yield was 34.7 g. Nitrogen content was 2 percent (dry basis).
- the product was gelatinized and dispersed in hot water and showed cationic activity.
- Example 4 25 grams of slightly oxidized starch prepared by pe riodate oxidation of corn starch to contain 3 percent dialdehyde content of theory was stirred in 75 ml. of water. To the stirred slurry was added 25 ml. of a water solution containing aminoguanidine hydrochloride prepared by acidification of 2.5 grams of aminoguanidine bicarbonate with hydrochloric acid. The reaction was carried out for 4 hours at 30 C. The white product was filtered and washed with water. After drying it weighed 24.5
- the product was dispersed in hot water and showed cationic activity.
- a cationic substantially fully oxidized starch hydrazone in which the carbonyl oxygens in about 5 percent of the originally present carbonyl groups in the periodate oxidized starch have been directly substituted by 2.
- a process for producing a cationic substantially fully oxidized starch hydrazone wherein about 5 percent of the carbonyl oxygens originally present in the periodateoxidized starch have been directly substituted by groups comprising reacting a periodateoxidized starch containing about 93 percent of theory of dialdehyde groups with about 10 percent, based on the weight of said starch, of a soluble salt of aminoguanidine in an aqueous medium at about pH 2-4 and a temperature of about 2540 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent Office 3,230,213 Patented Jan. 18, 1966 3,230,213 PRETARATIQN F AMENOGUANIDINE DERIVATIVES Charles L. Mehltretter, Peoria, 111., assignor to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed July 19, 1962, Ser. No. 211,140 2 Claims. (Cl. 260-2333) (Granted under Title 35, US. (lode (1052), see. 266) These novel guanylhydrazone are particularly valuable as cationic agents for retention of dyes and pigments on cellulosic fibers and as compositions, particularly with the guanylhydrazones of the more highly oxidized dialdehyde starch starting materials, for providing dry and wet strength in paper by addition to cellulosic fibers prior to sheet formation.
My novel guanylhydrazones gelatinize in hot water to produce dispersions which are positively charged and have a cationic efiect at various pH levels. They are thus substantive to negatively charged cellulosic fibers and to anionic pigments and dyes.
Conventional methods for preparing cationic starches which includes oxystarches of low degree of carbonyl content as described in U.S. Patents 2,876,217 and 2,917,- 506 involve the introduction of tertiary and quaternary nitrogen groups to the starch molecule by reaction of the free hydroxyl groups of starch with appropriate cationic substances under alkaline conditions. Cationic oxidized starches thus prepared generally have been severely degraded under the strongly alkaline conditions required to eifect reaction of the free hydroxyl groups in the oxidized starch. It is known that oxidized polysaccharides are readily susceptible to degradation with alkali through their carbonyl function. It is stated in Advances in Carbohydrate Chemistry, vol. 13, pages 316, 317
(1958), that the greater the carbonyl content of the polysaccharides starch or cellulose the greater is the molecular degradation in the presence of alkali.
I have discovered that products possessing cationic properties can be prepared by reacting the carbonyl groups in oxidized starches with soluble salts of aminoguanidine using aqueous acidic conditions. Under these conditions high yields of essentially colorless products are obtained with essentially no degradation of the oxidized starch molecule.
The presence of electropositive primary amino and imino groups in the products of the invention are believed to additively produce the exceptionally pronounced cat ionic properties observed in gelatinized dispersions of the ionized salts of the guanylhydrazones in water.
The main object of this invention is the synthesis of new cationic hydrazones containing both primary amino and imino groupings by reaction in water of oxidized starches containing reactive carbonyl groups with soluble aminoguanidine salts under acidic conditions. Partial substitution of the carbonyl groups in substantially fully oxidized starches is preferred for economic reasons. Further obiects will be apparent from the following detailed description.
These objects have been accomplished by reacting any water-soluble aminoguanidine salt with a water-insoluble oxidized starch in an acid aqueous system for at least one hour at a non-gelatinizing temperature Within the range of 25 to about 40 C. using up to one-fifth part by weight of the aminoguanidine salt per part of the oxidized starch but preferably 0.5 percent to about 10 percent by weight. The water-insoluble oxidized starch is continuously stirred in the acid aqueous reaction mixture and is reacted in the granule state. The white product is isolated by filtration and washed with water before drying. The yields are quantitative.
The carbonyl groups of the oxidized starches react with the aminoguanidine salts to form hydrazones. However, it is preferred to react only about 0.5 to 10 percent of the carbonyl groups present in the highly oxidized (dialdehyde) starches. Essentiallyallof-the carbonyl groups are preferred to be reacted in the oxystarches containing a low carbonyl content of up to about 6 percent, although only a portion of the carbonyl groups may be reacted. The highly oxidized starches as is Well known may be prepared by periodate oxidation of starch. The commercially available lowly oxidized starches are generally produced by hypochlorite or chlorine oxidation of corn starch or other starches such as those of potato, wheat, sorghum, and tapioca.
The following examples illustrate the invention.
Example 1 25 grams of dialdehyde starch (corn starch oxidized with periodic acid to 93 percent dialdehyde content) was stirred in ml. of water at room temperature. To the continuously stirred slurry was added 25 ml. of an aqueous solution of aminoguanidine hydrochloride prepared by acidification of 2.5 grams of commercial aminoguanidine bicarbonate with hydrochloric acid. The pH of the reaction mixture was about 3. Reaction was continued at room temperature for 16 hours when the mixture was filtered or centrifuged off. The white product was washed with water and then with methanol and dried at 40 C. overnight. The recovery of white product was 27.4 grams. Nitrogen content was 2.99 percent (dry basis). Moisture was 13.1 percent.
The nitrogen content showed that about 5 percent of the carbonyl groups of the dialdehyde starch had reacted with aminoguanidine hydrochloride to form a partial hydrazone.
3 percent dispersions of this product in water at C. for 30 minutes were fairly clear and only slightly viscous. Applications to cellulosic pulp showed good substantivity and gave the pulp a positive charge. Paper prepared with pulp treated with this product had good Wet strength and improved dry strength.
Example 2 Nitrogen to cellulosic pulp, and gave the pulp a positive charge. The treated pulp highly absorbed an anionic dye from solution.
Example 3 36 grams of a commercial hypochlorite oxidized starch was slurried in 100 m1. of water and 25 ml. of water containing aminoguanidine hydrochloride prepared by acidification of 2.72 grams of aminoguanidine bicarbonate to pH 2. The mixture was stirred at room temperature for 20 hours and filtered. After 2 washings with water the white product was dried at 40 C. The yield was 34.7 g. Nitrogen content was 2 percent (dry basis).
The product was gelatinized and dispersed in hot water and showed cationic activity.
Example 4 Example 5 25 grams of slightly oxidized starch prepared by pe riodate oxidation of corn starch to contain 3 percent dialdehyde content of theory was stirred in 75 ml. of water. To the stirred slurry was added 25 ml. of a water solution containing aminoguanidine hydrochloride prepared by acidification of 2.5 grams of aminoguanidine bicarbonate with hydrochloric acid. The reaction was carried out for 4 hours at 30 C. The white product was filtered and washed with water. After drying it weighed 24.5
grams and contained 2.5 percent nitrogen (dry basis). Essentially all of the aldehyde groups had reacted.
The product was dispersed in hot water and showed cationic activity.
I claim:
1. A cationic substantially fully oxidized starch hydrazone in which the carbonyl oxygens in about 5 percent of the originally present carbonyl groups in the periodate oxidized starch have been directly substituted by 2. A process for producing a cationic substantially fully oxidized starch hydrazone wherein about 5 percent of the carbonyl oxygens originally present in the periodateoxidized starch have been directly substituted by groups, said process comprising reacting a periodateoxidized starch containing about 93 percent of theory of dialdehyde groups with about 10 percent, based on the weight of said starch, of a soluble salt of aminoguanidine in an aqueous medium at about pH 2-4 and a temperature of about 2540 C.
References Cited by the Examiner UNITED STATES PATENTS 2,736,749 2/ 1956 Robinson 26069 2,822,312 2/ 1958 Bretscher et a1. 260-69 2,512,671 6/1950 Novotny et a1. 26069 3,098,869 7/1963 Borchert 260233.3
LEON J. BERCOVITZ, Primary Examiner.
JAMES A. SEIDLECK, Examiner.
I. M. DULIN, R. W. MULCAHY, Assistant Examiners.
Claims (1)
1. A CATIONIC SUBSTANTIALLY FULLY OXIDIZED STARCH HYDRAZONE IN WHICH THE CARBONYL OXYGENS IN ABOUT 5 PERCENT OF THE ORIGINALLY PRESENT CARBONYL GROUPS IN THE PERIODATE OXIDIZED STARCH HAVE BEEN DIRECTLY SUBSTITUTED BY
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US211140A US3230213A (en) | 1962-07-19 | 1962-07-19 | Preparation of aminoguanidine derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US211140A US3230213A (en) | 1962-07-19 | 1962-07-19 | Preparation of aminoguanidine derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3230213A true US3230213A (en) | 1966-01-18 |
Family
ID=22785726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US211140A Expired - Lifetime US3230213A (en) | 1962-07-19 | 1962-07-19 | Preparation of aminoguanidine derivatives |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3230213A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2130558A1 (en) * | 1971-03-25 | 1972-11-03 | Unilever Nv | |
| US8012907B2 (en) | 2004-09-14 | 2011-09-06 | Archer Daniels Midland Company | Guanidinated polysaccharides, their use as absorbents and process for producing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2512671A (en) * | 1945-08-08 | 1950-06-27 | Borden Co | Hemi-formalization products of urea-formaldehyde resinous condensates |
| US2736749A (en) * | 1952-06-10 | 1956-02-28 | Arnold Hoffman & Co Inc | Dye-fixing agents |
| US2822312A (en) * | 1952-05-07 | 1958-02-04 | Saul & Co | Microbicidal composition material impregnated therewith and method of impregnation |
| US3098869A (en) * | 1960-07-07 | 1963-07-23 | Miles Lab | Preparation of dialdehyde polysaccharide addition products |
-
1962
- 1962-07-19 US US211140A patent/US3230213A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2512671A (en) * | 1945-08-08 | 1950-06-27 | Borden Co | Hemi-formalization products of urea-formaldehyde resinous condensates |
| US2822312A (en) * | 1952-05-07 | 1958-02-04 | Saul & Co | Microbicidal composition material impregnated therewith and method of impregnation |
| US2736749A (en) * | 1952-06-10 | 1956-02-28 | Arnold Hoffman & Co Inc | Dye-fixing agents |
| US3098869A (en) * | 1960-07-07 | 1963-07-23 | Miles Lab | Preparation of dialdehyde polysaccharide addition products |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2130558A1 (en) * | 1971-03-25 | 1972-11-03 | Unilever Nv | |
| US8012907B2 (en) | 2004-09-14 | 2011-09-06 | Archer Daniels Midland Company | Guanidinated polysaccharides, their use as absorbents and process for producing same |
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